Capacitor, semiconductor device including the same, and method of fabricating capacitor

ABSTRACT

A capacitor includes: a bottom electrode; a top electrode over the bottom electrode; a dielectric film between the bottom electrode and the top electrode; and a doped Al 2 O 3  film between the top electrode and the dielectric film, wherein the doped Al 2 O 3  film includes a first dopant, and an oxide including the same element as the first dopant has a higher dielectric constant than a dielectric constant of Al 2 O 3 .

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. Application No. 17/060,911,filed Oct. 1, 2020, which claims the benefit of Korean PatentApplication No. 10-2020-0023706, filed on Feb. 26, 2020, in the KoreanIntellectual Property Office, the disclosure of each of which isincorporated herein in its entirety by reference.

BACKGROUND 1. Field

The present disclosure relates to capacitors, semiconductor devices, andmethods of fabricating capacitors.

2. Description of Related Art

Along with down-scaling of integrated circuit devices, spaces occupiedby capacitors have been reduced. Capacitors include top and bottomelectrodes and dielectric films between these electrodes and employdielectric materials having high dielectric constants to exhibit highcapacitance. Leakage current may flow through the insides of capacitors.Techniques for reducing and/or minimizing a reduction in capacitancewhile reducing leakage current flowing through the insides of capacitorsmay be needed.

SUMMARY

Provided are capacitors having excellent leakage current blockingproperties and having high capacitance.

Provided are semiconductor devices which include capacitors havingexcellent leakage current blocking properties and having highcapacitance.

Provided are methods of fabricating capacitors which have excellentleakage current blocking properties and have high capacitance.

However, the present disclosure is not limited to the aspects set forthabove.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description, or may belearned by practice of the presented embodiments of the disclosure.

According to an aspect of an embodiment, a capacitor includes: a bottomelectrode; a top electrode over the bottom electrode; a dielectric filmbetween the bottom electrode and the top electrode; and a doped Al₂O₃film between the top electrode and the dielectric film. The doped Al₂O₃film includes a first dopant, and an oxide including a same element asthe first dopant has a higher dielectric constant than a dielectricconstant of Al₂O₃.

In some embodiments, the first dopant may include one of Ca, Sr, Ba, Sc,Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu.

In some embodiments, the doped Al₂O₃ film may include the first dopantin an amount greater than 0% and less than 50 at%.

In some embodiments, the doped Al₂O₃ film may further include a seconddopant that is different from the first dopant, and an oxide including asame element as the second dopant may have a higher dielectric constantthan the dielectric constant of Al₂O₃.

In some embodiments, the second dopant may include one of Ca, Sr, Ba,Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu.

In some embodiments, the first dopant and the second dopant may bepresent in an amount greater than 0 at % and less than 50 at% in totalin the doped Al₂O₃ film.

In some embodiments, the bottom electrode may directly contact thedielectric film.

In some embodiments, the capacitor may further include an interfacialfilm between the bottom electrode and the dielectric film, and theinterfacial film may include an oxide including a metal element that isincluded in the bottom electrode.

In some embodiments, the bottom electrode may include a metal nitriderepresented by MM′N, and the interfacial film may include a metaloxynitride represented by MM′ON, wherein M may be a metal element, M′may be an element different from M, N may be nitrogen, and O may beoxygen.

In some embodiments, the bottom electrode may include carbon impuritiesin an amount greater than 0% and less than or equal to 1%.

In some embodiments, M may be Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh,Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg, Tl, Pb, Bi,Po, Fr, Ra, Ac, Th, Pa, or U.

In some embodiments, M′ may be H, Li, Be, B, N, O, Na, Mg, Al, Si, P, S,K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y,Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr,Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr,Pt, Au, Hg, Tl, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, or U.

In some embodiments, the metal nitride may be represented byM_(x)M_(′y)N_(z) where 0<×≤2, 0<y≤2, and 0<z≤4 may be satisfied.

In some embodiments, the dielectric film may have a thickness of greaterthan 0 nm and less than 5 nanometers (nm), and the doped Al₂O₃ film mayhave a thickness of greater than 0 nm and less than 2 nm.

In some embodiments, the top electrode may directly contact a topsurface of the doped Al₂O₃ film, and the dielectric film may directlycontact a bottom surface of the doped Al₂O₃ film.

In some embodiments, the top electrode may include TiN, MoN, CoN, TaN,TiAlN, TaAlN, W, Ru, RuO₂, SrRuO₃, Ir, lrO₂, Pt, PtO, (Ba,Sr)RuO₃(BSRO), CaRuO₃ (CRO), (La,Sr)CoO₃ (LSCO), or a combination thereof.

According to an aspect of another embodiment, a semiconductor deviceincludes: a substrate; a gate structure on the substrate; a firstsource/drain region and a second source/drain region, both arranged inupper portions of the substrate; and a capacitor on the substrate. Thecapacitor includes a bottom electrode, a top electrode, a dielectricfilm between the bottom electrode and the top electrode, and a dopedAl2O3 film between the top electrode and the dielectric film. The bottomelectrode is electrically connected to the first source/drain region.The top electrode is over the bottom electrode. The doped Al₂O₃ filmincludes a first dopant. An oxide including a same element as the firstdopant has a higher dielectric constant than a dielectric constant ofAl₂O₃.

In some embodiments, the doped Al₂O₃ film may further include a seconddopant that is different from the first dopant. An oxide including asame element as the second dopant may have a higher dielectric constantthan the dielectric constant of Al₂O₃.

In some embodiments, the first dopant and the second dopant may beselected from different elements among Ca, Sr, Ba, Sc, Y, La, Ti, Hf,Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu.

In some embodiments, the doped Al₂O₃ film may include the first dopantand the second dopant in an amount greater than 0 at % and less than 50at% in total.

In some embodiments, the bottom electrode may include a metal nitriderepresented by MM′N, wherein M may be a metal element, M′ may be anelement different from M, N may be nitrogen, and O may be oxygen.

In some embodiments, M may be Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh,Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg, Tl, Pb, Bi,Po, Fr, Ra, Ac, Th, Pa, or U. M′ may be H, Li, Be, B, N, O, Na, Mg, Al,Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se,Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W,Re, Os, lr, Pt, Au, Hg, Tl, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, or U.

In some embodiments, the metal nitride may be represented by M×M′yNz,where 0<x≤2, 0<y≤2, and 0<z≤4 may be satisfied.

In some embodiments, the top electrode may directly contact a topsurface of the doped Al₂O₃ film, and the dielectric film may directlycontact a bottom surface of the doped Al₂O₃ film.

According to another embodiment, a method of fabricating a capacitorincludes: forming a bottom electrode; forming a dielectric film on thebottom electrode; forming a doped Al₂O₃ film on the dielectric film; andforming a top electrode on the doped Al₂O₃ film. The doped Al₂O₃ filmincludes a first dopant. An oxide including a same element as the firstdopant has a higher dielectric constant than a dielectric constant ofAl₂O₃.

In some embodiments, the forming the doped Al₂O₃ film may includeforming an Al₂O₃ film on the dielectric film and performing a heattreatment on the dielectric film and the Al₂O₃ film. The dielectric filmmay include an oxide of an element that is the same as the first dopant.The performing the heat treatment may include diffusing the element thatis the same as the first dopant from the dielectric film into the Al₂O₃film by the heat treatment to provide the doped Al₂O₃ film by the heattreatment to provide the doped Al₂O₃ film. The first dopant may be Ca,Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, or Lu.

In some embodiments, the forming the doped Al₂O₃ film may include:depositing Al, O, and a same element as the first dopant on thedielectric film by an in-situ process, wherein the same element as thefirst dopant may be Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr,Nd, Gd, Dy, Yb, or Lu.

In some embodiments, the doped Al₂O₃ film may further include a seconddopant that is different from the first dopant, and an oxide including asame element as the second dopant may have a higher dielectric constantthan the dielectric constant of Al₂O₃.

In some embodiments, the forming the doped Al₂O₃ film may include:forming an additional oxide film on the dielectric film; forming anAl₂O₃ film on the additional oxide film, performing a heat treatment.The heat treatment may be performed on the dielectric film, theadditional oxide film, and the Al₂O₃ film. The dielectric film and theadditional oxide film may respectively include oxides including twodifferent elements selected from among Ca, Sr, Ba, Sc, Y, La, Ti, Hf,Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu. The two elements, which areselected from among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr,Nd, Gd, Dy, Yb, and Lu and are respectively in the dielectric film andthe additional oxide, may be diffused into the Al₂O₃ film by the heattreatment. The first dopant and the second dopant may be respectivelythe two elements selected from among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr,Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu and diffused into the Al₂O₃ film.

In some embodiments, the doped Al₂O₃ film may include the first dopantand the second dopant in an amount greater than 0 at % and less than 50at% in total.

In some embodiments, the forming the bottom electrode may include:arranging a substrate in a reaction chamber; supplying a first sourceincluding a metal organic ligand into the reaction chamber; performing afirst purging for removing an organic ligand of the first source that isnot adsorbed onto the substrate; supplying a second source including ahalogen compound into the reaction chamber; performing second purgingfor removing the organic ligand that has not reacting with the secondsource; and supplying a nitridant into the reaction chamber.

In some embodiments, the metal organic ligand may be represented byMR_(x) (where M may be a metal element, M, and R may be an organicligand), wherein x may be in a range of 0 < x ≤ 6.

In some embodiments, M may be Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh,Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg, Tl, Pb, Bi,Po, Fr, Ra, Ac, Th, Pa, or U.

In some embodiments, R may include at least one of a C1-C10 alkyl group,a C2-C10 alkenyl group, a carbonyl group (C═O), a halide, a C6-C10 arylgroup, a C6-C10 cycloalkyl group, a C6-C10 cycloalkenyl group, (C═O)R(where R is hydrogen or a C1-C10 alkyl group), a C1-C10 alkoxy group, aC1-C10 amidinate, a C1-C10 alkylamide, a C1-C10 alkylimide, —N(Q)(Q′)(where Q and Q′ are each independently a C1-C10 alkyl group orhydrogen), Q(C═O)CN (where Q is hydrogen or a C1-C10 alkyl group), and aC1-C10 β-diketonate.

In some embodiments, halogen compound may be represented by M′A_(y)(where y is a real number greater than 0 and A may be a halogen element.M′ may be H, Li, Be, B, N, O, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc,Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg, Tl,Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, or U.

In some embodiments, A may include at least one of F, Cl, Br, and l, andy may be in a range of 0<y≤6.

In some embodiments, the supplying the first source, the supplying thesecond source, and the supplying the nitridant may be performed using anatomic layer deposition (ALD) process.

In some embodiments, the nitridant may include at least one of NH₃,N₂H₂, N₃H, and N₂H₄.

In some embodiments, the method set forth above may further includeperforming a heat treatment for removing the halogen element of thehalogen compound, the halogen element remaining as a reactionby-product.

In some embodiments, the bottom electrode may include carbon impuritiesin an amount greater than 0% and less than or equal to 1%.

According to an embodiment, a capacitor includes a bottom electrode; atop electrode over the bottom electrode; a dielectric film between thebottom electrode and the top electrode; and a doped Al₂O₃ film betweenthe top electrode and the dielectric film. The doped Al₂O₃ film mayinclude a first dopant. An oxide of first dopant may have a dielectricconstant that is higher than a dielectric constant of Al₂O₃.

In some embodiments, the doped Al₂O₃ film may further include a seconddopant that is different from the first dopant. An oxide of seconddopant may have a dielectric constant that is higher than a dielectricconstant of Al₂O₃, The first dopant and the second dopant may bedifferent elements among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce,Pr, Nd, Gd, Dy, Yb, or Lu. The dielectric film may include an oxide ofthe first dopant, an oxide of the second dopant, or both the oxide ofthe first dopant and the oxide of the second dopant.

In some embodiments, the dielectric film may include a first region anda second region. The first region may include the oxide of the firstdopant. The second region may include the oxide of the second dopant.The second region of the dielectric film may be between the first regionof the dielectric film and the doped Al₂O₃ film.

In some embodiments, a semiconductor device may include one of theabove-described capacitors.

In some embodiments, a semiconductor device may include one of theabove-described capacitors.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other aspects, features, and effects of certainembodiments of the disclosure will be more apparent from the followingdescription taken in conjunction with the accompanying drawings, inwhich:

FIG. 1 is a cross-sectional view of a capacitor according to an exampleembodiment;

FIG. 2 illustrates normalized capacitance change graphs;

FIG. 3 illustrates leakage current change graphs;

FIG. 4 is a cross-sectional view of a capacitor according to an exampleembodiment;

FIG. 5 is a cross-sectional view of a semiconductor device according toan example embodiment;

FIG. 6 is a cross-sectional view of a semiconductor device according toan example embodiment;

FIG. 7 is a cross-sectional view illustrating a method of fabricatingthe capacitor of FIG. 1 ;

FIG. 8 is a cross-sectional view illustrating a method of fabricatingthe capacitor of FIG. 1 ;

FIG. 9 is a cross-sectional view illustrating a method of fabricatingthe capacitor of FIG. 1 ;

FIG. 10 is a flowchart illustrating a method of manufacturing a bottomelectrode that includes a metal nitride represented by MM′N;

FIG. 11A is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11B is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11C is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11D is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11E is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11F is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11G is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 11H is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 ;

FIG. 12 is a schematic diagram for an electronic device including acapacitor according to some embodiments; and

FIG. 13 is a schematic diagram of a memory system including a capacitoraccording to some embodiments.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments, examples of whichare illustrated in the accompanying drawings, wherein like referencenumerals refer to like elements throughout. In this regard, the presentembodiments may have different forms and should not be construed asbeing limited to the descriptions set forth herein. Accordingly, theembodiments are merely described below, by referring to the figures, toexplain aspects. As used herein, the term “and/or” includes any and allcombinations of one or more of the associated listed items. Expressionssuch as “at least one of,” when preceding a list of elements, modify theentire list of elements and do not modify the individual elements of thelist. For example, “at least one of A, B, and C,” “at least one of A, B,or C,” “one of A, B, C, or a combination thereof,” and “one of A, B, C,and a combination thereof,” respectively, may be construed as coveringany one of the following combinations: A; B; C; A and B; A and C; B andC; and A, B, and C.”

Hereinafter, embodiments of the present disclosure will be described indetail with reference to the accompanying drawings. Like components willbe denoted by like reference numerals throughout the specification, andin the drawings, the size of each component may be exaggerated forclarity and convenience of descriptions. It should be understood thatembodiments described below are provided for illustrative purposes onlyand that various changes and modifications can be made to theseembodiments.

It will be understood that, when an element is referred to as beingplaced “on” another element, it can be directly placed on the otherelement, or an intervening layer(s) may also be present.

As used herein, the singular terms “a,” “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be understood that the terms such as “comprises”,“comprising”, “includes”, “including”, “has”, and “having”, when usedherein, specify the presence of stated components, but do not precludethe presence or addition of other components, unless clearly statedotherwise.

As used herein, the terms “part,” “module,” and the like refers to aunit for performing at least one function or operation, and such a theunit may be implemented by hardware, software, or a combination ofhardware and software.

FIG. 1 is a cross-sectional view of a capacitor according to an exampleembodiment.

Referring to FIG. 1 , a capacitor 1 may be provided. The capacitor 1 mayinclude a bottom electrode 100, a dielectric film 200, a doped Al₂O₃film 300, and a top electrode 400. A material of the bottom electrode100 may be selected to secure conductivity for use as an electrode andto maintain stable capacitance performance even after a high temperatureprocess during a process of fabricating the capacitor 1.

In an example, the bottom electrode 100 may include a metal, a metalnitride, a metal oxide, or a combination thereof. For example, the topelectrode 400 may include TiN, MoN, CoN, TaN, W, Ru, RuO₂, SrRuO₃, Ir,IrO₂, Pt, PtO, (Ba,Sr)RuO₃ (BSRO), CaRuO₃ (CRO), (La,Sr)CoO₃ (LSCO), ora combination thereof.

For example, the bottom electrode 100 may include a metal nitriderepresented by MM′N. Here, M is a metal element, M′ is an element thatis different from M, and N is nitrogen. The metal nitride, that is,MM′N, which constitutes the bottom electrode 100, may also be describedas being obtained by doping a metal nitride, MN, with an element, M′.M′, which is an element different from M, may be a metal, but is notlimited thereto, and may be a material other than a metal.

M may be one of Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co,Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In,Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg, Tl, Pb, Bi, Po, Fr, Ra, Ac,Th, Pa, and U.

M′ may be one of H, Li, Be, B, N, O, Na, Mg, Al, Si, P, S, K, Ca, Sc,Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb,Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au,Hg, Tl, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, and U. When a composition ratioof M to M′ to N in the metal nitride, MM′N, is x:y:z (e.g., the metalnitride may be M_(x)M_(′y)N_(z)), 0<×≤2, 0<y≤2, and 0<z≤4 may besatisfied. Electrical properties as well as electrical conductivity ofthe capacitor 1 may vary depending upon the composition ratio. Thecomposition ratio is a factor that also influences a materialcomposition of an interfacial film 500 (see FIG. 4 ), and this isbecause the interfacial film 500 is a main cause of a change incapacitance according to bias voltages. The composition ratio may varyaccording to specific selections of M and M′.

In an atomic layer deposition (ALD) process generally used tomanufacture a metal nitride, as a source of a metal material, a metalorganic ligand material is used as a precursor. Here, when an organicligand is not sufficiently removed after the metal material is appliedonto a target surface, carbon impurities are included in a metal nitridefilm, and this may be a cause of deterioration in performance of acapacitor. In the capacitor 1 according to an embodiment, as describedabove, the metal nitride, MM′N, is used as a material of the bottomelectrode 100, and according to a manufacturing method described below,the metal nitride, MM′N, having almost no carbon impurities is employedfor the bottom electrode 100. The bottom electrode 100 may includecarbon in an amount of 1% or less and greater than 0%.

The dielectric film 200 may be arranged on the bottom electrode 100. Thedielectric film 200 may directly contact the bottom electrode 100. Thedielectric film 200 may include a material capable of implementingdesired capacitance. Along with increasing degrees of integration ofintegrated circuit devices including the capacitor 1, a space occupiedby the capacitor 1 gradually decreases, and thus, a dielectric having ahigh dielectric constant may be used. The dielectric film 200 mayinclude a high-dielectric constant (high-k) material. A high dielectricconstant denotes a dielectric constant that is higher than thedielectric constant of silicon oxide. The dielectric film 200 mayinclude a metal oxide including at least one metal selected from amongCa, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, andLu. For example, the dielectric film 200 may include HfO₂, ZrO₂, CeO₂,La₂O₃, Ta₂O₃, or TiO₂. Although the dielectric film 200 may have asingle-layer structure as illustrated, the dielectric film 200 is notlimited thereto and may have a multilayer structure. The dielectric film200 may have a thickness allowing desired capacitance to be implemented.For example, the dielectric film 200 may have a thickness less than 5nm.

The doped Al₂O₃ film 300 may be arranged on the dielectric film 200. Thedoped Al₂O₃ film 300 may block or reduce flow of leakage current betweenthe top electrode 400 and the bottom electrode 100. That is, the dopedAl₂O₃ film 300 may be a leakage current reducing layer. In an example,the doped Al₂O₃ film 300 may include a first dopant. The first dopantmay be determined such that a dielectric constant of an oxide includingthe same element as the first dopant is higher than the dielectricconstant of Al₂O₃. For example, the first dopant may be one selectedfrom among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd,Dy, Yb, and Lu. The doped Al₂O₃ film 300 may include the first dopant inan amount less than 50 at%. In an example, the doped Al₂O₃ film 300 mayfurther include a second dopant that is different from the first dopant.The second dopant may be determined such that a dielectric constant ofan oxide including the same element as the second dopant is higher thanthe dielectric constant of Al₂O₃. For example, the second dopant may beone selected from among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce,Pr, Nd, Gd, Dy, Yb, and Lu. In the doped Al₂O₃ film 300, the firstdopant and the second dopant may be present in an amount less than 50at% in total. The doped Al₂O₃ film 300 is not limited to including, as adopant, only one type of element or two types of elements. In anotherexample, the doped Al₂O₃ film 300 may further include at least one typeof dopant that is different from the first and second dopants. Forexample, the doped Al₂O₃ film 300 may have a thickness less than 2 nm.

The top electrode 400 may be arranged on the doped Al₂O₃ film 300. Thetop electrode 400 may include a metal, a metal nitride, a metal oxide,or a combination thereof. For example, the top electrode 400 may includeTiN, MoN, CoN, TaN, TiAlN, TaAlN, W, Ru, RuO₂, SrRuO₃, Ir, IrO₂, Pt,PtO, (Ba,Sr)RuO₃ (BSRO), CaRuO₃ (CRO), (La,Sr)CoO₃ (LSCO), or acombination thereof.

Unlike the present disclosure, when an undoped Al₂O₃ film is arrangedbetween the top electrode 400 and the dielectric film 200, althoughleakage current may be reduced, the capacitance of the capacitor may bereduced. The doped Al₂O₃ film 300 of the present disclosure may limitand/or minimize a reduction in capacitance while having a leakagecurrent blocking property that is similar to that of an undoped Al₂O₃film.

Unlike the present disclosure, when an undoped Al₂O₃ film or a dopedAl₂O₃ film is arranged between the dielectric film 200 and the bottomelectrode 100, crystallinity of the dielectric film 200 may be reduceddue to deterioration in induction, performed by the bottom electrode100, of the crystallinity of the dielectric film 200. Accordingly, thecapacitance of the capacitor may be reduced. The doped Al₂O₃ film 300 ofthe present disclosure may be arranged between the dielectric film 200and the top electrode 400 and thus may not reduce the crystallinity ofthe dielectric film 200. Accordingly, the capacitance of the capacitormay not be reduced.

FIG. 2 illustrates normalized capacitance change graphs. FIG. 3illustrates leakage current change graphs.

Referring to FIG. 2 , a normalized capacitance change graph ① in thecase where the doped Al₂O₃ film 300 was removed from the capacitor 1 ofFIG. 1 , a normalized capacitance change graph ② of the capacitor 1 ofFIG. 1 , a normalized capacitance change graph ③ in the case where anundoped Al₂O₃ film, instead of the doped Al₂O₃ film 300, was applied tothe capacitor 1 of FIG. 1 , and a normalized capacitance change graph ④in the case where, in the capacitor 1 of FIG. 1 , the doped Al₂O₃ film300 was arranged between the bottom electrode 100 and the dielectricfilm 200 rather than between the top electrode 400 and the dielectricfilm 200 are provided.

As compared with the case where the doped Al₂O₃ film 300 was removedfrom the capacitor 1 of FIG. 1 (graph ①), there was a greatest reductionin capacitance in the case where, in the capacitor 1 of FIG. 1 , thedoped Al₂O₃ film 300 was arranged between the bottom electrode 100 andthe dielectric film 200 rather than between the top electrode 400 andthe dielectric film 200 (graph ④).

In the case where an undoped Al₂O₃ film, instead of the doped Al₂O₃ film300, was applied to the capacitor 1 of FIG. 1 (graph ③), the reductionin capacitance was smaller than in the case where, in the capacitor 1 ofFIG. 1 , the doped Al₂O₃ film 300 was arranged between the bottomelectrode 100 and the dielectric film 200 rather than between the topelectrode 400 and the dielectric film 200 (graph ④).

In the case of the capacitor 1 of FIG. 1 (graph ②), the reduction incapacitance was smallest.

Referring to FIG. 3 , a leakage current change graph ⓐ in the case wherethe doped Al₂O₃ film 300 was removed from the capacitor 1 of FIG. 1 , aleakage current change graph ⓑ of the capacitor 1 of FIG. 1 , and aleakage current change graph ⓒ in the case where an undoped Al₂O₃ film,instead of the doped Al₂O₃ film 300, was applied to the capacitor 1 ofFIG. 1 are provided.

As compared with the case where the doped Al₂O₃ film 300 was removedfrom the capacitor 1 of FIG. 1 (graph ⓐ), the reduction in leakagecurrent in the case of the capacitor 1 of FIG. 1 (graph ⓑ) was similarto the reduction in leakage current in the case where an undoped Al₂O₃film, instead of the doped Al₂O₃ film 300, was applied to the capacitor1 of FIG (graph ⓒ).

The doped Al₂O₃ film 300 of the present disclosure may limit and/orminimize the reduction in capacitance of the capacitor 1 while having aleakage current reducing property similar to that of an undoped Al₂O₃film.

FIG. 4 is a cross-sectional view of a capacitor according to an exampleembodiment. For simplicity of descriptions, substantially the samedescriptions as those given with reference to FIG. 1 may be omitted.

Referring to FIG. 4 , a capacitor 2 may be provided. The capacitor 2 mayinclude a bottom electrode 100, an interfacial film 500, a dielectricfilm 200, a doped Al₂O₃ film 300, and a top electrode 400. The bottomelectrode 100, the dielectric film 200, the doped Al₂O₃ film 300, andthe top electrode 400 may be respectively and substantially the same asthe bottom electrode 100, the dielectric film 200, the doped Al₂O₃ film300, and the top electrode 400, which have been described with referenceto FIG. 1 .

The interfacial film 500 may be arranged between the bottom electrode100 and the dielectric film 200. The interfacial film 500 may include ametal oxide including a metal element that is included in the bottomelectrode 100. When the bottom electrode 100 includes a metal nitriderepresented by MM′N, the interfacial film 500 may include a metaloxynitride represented by MM′ON. Here, M is a metal element included inthe bottom electrode 100, M′ is an element included in the bottomelectrode 100 and different from M, N is nitrogen, and O is oxygen.Example materials of M and M′ may be substantially the same as thosedescribed with reference with FIG. 1 . The thickness of the interfacialfilm 500 may be less than the thickness of the bottom electrode 100. Theinterfacial film 500 may include carbon impurities in an amount of 1% orless.

FIG. 5 is a cross-sectional view of a semiconductor device according toan example embodiment. For simplicity of descriptions, substantially thesame descriptions as those given with reference to FIG. 1 may beomitted.

Referring to FIG. 5 , a semiconductor device 11 including a substrate1100, a gate structure 1300, an interlayer dielectric 1400, a contact1500, and a capacitor 1 may be provided. The substrate 1100 may includea semiconductor substrate. For example, the substrate 1100 may include asilicon substrate, a germanium substrate, or a silicon-germaniumsubstrate.

A first source/drain region 1210 and a second source/drain region 1220may be arranged in upper portions of the substrate 1100. The first andsecond source/drain regions 1210 and 1220 may be apart from each otherin a first direction DR1 that is parallel to a top surface of thesubstrate 1100. The first and second source/drain regions 1210 and 1220may be formed by implanting impurities into the substrate 1100.

The gate structure 1300 may be arranged on the substrate 1100. The gatestructure 1300 may be arranged between the first and second source/drainregions 1210 and 1220. The gate structure 1300 may include a gateelectrode 1310 and a gate insulating film 1320. The gate electrode 1310may include a conductive material. For example, the gate electrode 1310may include a metal or polysilicon.

The gate insulating film 1320 may be arranged between the gate electrode1310 and the substrate 1100. The gate insulating film 1320 mayelectrically insulate the substrate 1100 from the gate electrode 1310.The gate insulating film 1320 may include a dielectric material. Forexample, the gate insulating film 1320 may include a Si oxide (forexample, SiO₂), an Al oxide (for example, Al₂O₃), or a high-k material(for example, HfO₂).

The interlayer dielectric 1400 may be arranged on the substrate 1100 tocover the gate structure 1300. The interlayer dielectric 1400 mayinclude an insulating material. For example, the interlayer dielectric1400 may include a Si oxide (for example, SiO₂), an Al oxide (forexample, Al₂O₃), or a high-K material (for example, HfO₂).

The capacitor 1 may be arranged on the interlayer dielectric 1400. Thecapacitor 1 may include a bottom electrode 100, a top electrode 400, adielectric film 200, and a doped Al₂O₃ film 300. The bottom electrode100, the top electrode 400, the dielectric film 200, and the doped Al₂O₃film 300 may be respectively and substantially the same as the bottomelectrode 100, the top electrode 400, the dielectric film 200, and thedoped Al₂O₃ film 300, which have been described with reference to FIG. 1.

The contact 1500 may be arranged between the bottom electrode 100 andthe first source/drain region 1210. The contact 1500 may penetrate theinterlayer dielectric 1400. The contact 1500 may electrically connectthe bottom electrode 100 to the first source/drain region 1210. Thecontact 1500 may include a conductive material (for example, a metal).

The doped Al₂O₃ film 300 may limit and/or minimize a reduction incapacitance of a capacitor while having a leakage current blockingproperty similar to that of an undoped Al₂O₃ film. The capacitor 1 ofthe present disclosure may include the doped Al₂O₃ film 300 as a leakagecurrent reducing layer. Accordingly, the stability and reliability ofthe semiconductor device 11 may be improved.

FIG. 6 is a cross-sectional view of a semiconductor device according toan example embodiment. For simplicity of descriptions, substantially thesame descriptions as those given with reference to FIGS. 1, 4, and 5 maybe omitted.

Referring to FIG. 6 , a semiconductor device 12 including a substrate1100, a gate structure 1300, an interlayer dielectric 1400, a contact1500, and a capacitor 2 may be provided. The substrate 1100, the gatestructure 1300, the interlayer dielectric 1400, and the contact 1500 maybe respectively and substantially the same as the substrate 1100, thegate structure 1300, the interlayer dielectric 1400, and the contact1500, which have been described with reference to FIG. 5 .

The capacitor 2 may be arranged on the interlayer dielectric 1400. Thecapacitor 2 may include a bottom electrode 100, an interfacial film 500,a top electrode 400, a dielectric film 200, and a doped Al₂O₃ film 300.The bottom electrode 100, the top electrode 400, the dielectric film200, and the doped Al₂O₃ film 300 may be respectively and substantiallythe same as the bottom electrode 100, the top electrode 400, thedielectric film 200, and the doped Al₂O₃ film 300, which have beendescribed with reference to FIG. 1 . The interfacial film 500 may besubstantially the same as the interfacial film 500 described withreference to FIG. 4 .

The doped Al₂O₃ film 300 may limit and/or minimize a reduction incapacitance of a capacitor while having a leakage current blockingproperty similar to that of an undoped Al₂O₃ film. The capacitor 2 ofthe present disclosure may include the doped Al₂O₃ film 300 as a leakagecurrent reducing layer. Accordingly, the stability and reliability ofthe semiconductor device 12 may be improved.

FIG. 7 is a cross-sectional view illustrating a method of fabricatingthe capacitor of FIG. 1 . FIG. 8 is a cross-sectional view illustratinga method of fabricating the capacitor of FIG. 1 .

Referring to FIG. 7 , the bottom electrode 100 and the dielectric film200 may be sequentially formed on a substrate SU in this stated order.The substrate SU may include a semiconductor material pattern, aninsulating material pattern, and a conductive material pattern. Forexample, the substrate SU may include the substrate 1100, the gatestructure 1300, the interlayer dielectric 1400, and the contact 1500 ofFIGS. 5 and 6 .

The bottom electrode 100 may be formed on the substrate SU by adeposition process. For example, a process of forming the bottomelectrode 100 may include a chemical vapor deposition (CVD) process, aphysical vapor deposition (PVD) process, or an atomic layer deposition(ALD) process. The bottom electrode 100 may include a metal, a metalnitride, a metal oxide, or a combination thereof. For example, thebottom electrode 100 may include TiN, MoN, CoN, TaN, W, Ru, RuO₂,SrRuO₃, Ir, lrO₂, Pt, PtO, (Ba,Sr)RuO₃ (BSRO), CaRuO₃ (CRO), (La,Sr)CoO₃(LSCO), or a combination thereof. A method of manufacturing the bottomelectrode 100 when the bottom electrode 100 includes a metal nitriderepresented by MM′N will be described below in detail.

The dielectric film 200 may be deposited on the bottom electrode 100.For example, the dielectric film 200 may be formed by a CVD process, aPVD process, or an ALD process. The dielectric film 200 may include ahigh-k material. For example, the dielectric film 200 may include ametal oxide including at least one metal selected from among Ca, Sr, Ba,Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu. Forexample, the dielectric film 200 may include HfO₂, ZrO₂, CeO₂, La₂O₃,Ta₂O₃, or TiO₂.

Referring to FIG. 8 , an undoped Al₂O₃ film 302 may be formed on thedielectric film 200. The undoped Al₂O₃ film 302 may be formed by adeposition process. For example, the undoped Al₂O₃ film 302 may beformed by a CVD process, a PVD process, or an ALD process.

During the process of forming the undoped Al₂O₃ film 302, or after thecompletion of the process of forming the undoped Al₂O₃ film 302, a heattreatment process H may be performed. By the heat treatment process H, ametal element in the dielectric film 200 may be diffused into theundoped Al₂O₃ film 302. For example, at least one selected from amongCa, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, andLu, in the dielectric film 200, may be diffused into the undoped Al₂O₃film 302. The heat treatment process H allows the undoped Al₂O₃ film 302to be doped with the diffused metal element, thereby forming the dopedAl₂O₃ film 300 described with reference to FIG. 1 . In other words, thedoped Al₂O₃ film 300 may be doped with the diffused metal element.However, a process of forming the doped Al₂O₃ film 300 is not limited tothe example set forth above. In another example, elements (aluminum (Al)and oxygen (O)) constituting an Al₂O₃ film and an element (for example,hafnium (Hf) and/or zirconium (Zr)) required to be doped into the Al₂O₃film may be deposited in situ by an ALD process, thereby forming thedoped Al₂O₃ film 300. The doped Al₂O₃ film 300 may include one type ofdopant (for example, the first dopant described with reference to FIG. 1).

Referring again to FIG. 1 , the top electrode 400 may be formed on thedoped Al₂O₃ film 300. The top electrode 400 may be formed by adeposition process. For example, the top electrode 400 may be formed bya CVD process, a PVD process, or an ALD process. The top electrode 400may include a metal, a metal nitride, a metal oxide, or a combinationthereof. For example, the top electrode 400 may include TiN, MoN, CoN,TaN, W, Ru, RuO₂, SrRuO₃, Ir, lrO₂, Pt, PtO, (Ba,Sr)RuO₃ (BSRO), CaRuO₃(CRO), (La,Sr)CoO₃ (LSCO), or a combination thereof.

The present disclosure may provide a method of fabricating the capacitor1 that includes the doped Al₂O₃ film 300 including one type of dopant.

FIG. 9 is a cross-sectional view illustrating a method of fabricatingthe capacitor of FIG. 1 . For simplicity of descriptions, substantiallythe same descriptions as those given with reference to FIGS. 7 and 8 maybe omitted.

The bottom electrode 100 and the dielectric film 200 may be formed onthe substrate SU by substantially the same process as that describedwith reference to FIG. 7 . Referring to FIG. 9 , an additional oxidefilm 200 a may be formed on the dielectric film 200. For example, theadditional oxide film 200 a may be formed by a CVD process, a PVDprocess, or an ALD process. The additional oxide film 200 a may includea high-k material. For example, the additional oxide film 200 a mayinclude a metal oxide including at least one metal, which is selectedfrom among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta, Ce, Pr, Nd, Gd,Dy, Yb, and Lu while not included in the dielectric film 200. Forexample, the additional oxide film 200 a may include HfO₂, ZrO₂, CeO₂,La₂O₃, Ta₂O₃, or TiO₂. The dielectric film 200 and additional oxide film200 a may provide a dielectric film structure where dielectric film 200is a first region and the additional oxide film 200 a is a secondregion.

The undoped Al₂O₃ film 302 may be formed on the additional oxide film200 a. The undoped Al₂O₃ film 302 may be formed by a deposition process.For example, the undoped Al₂O₃ film 302 may be formed by a CVD process,a PVD process, or an ALD process.

During the process of forming the undoped Al₂O₃ film 302, or after thecompletion of the process of forming the undoped Al₂O₃ film 302, theheat treatment process H may be performed. By the heat treatment processH, a metal element in the dielectric film 200 and a metal element in theadditional oxide film 200 a may be diffused into the undoped Al₂O₃ film302. For example, one selected from among Ca, Sr, Ba, Sc, Y, La, Ti, Hf,Zr, Nb, Ta, Ce, Pr, Nd, Gd, Dy, Yb, and Lu, in the dielectric film 200,and one selected from among Ca, Sr, Ba, Sc, Y, La, Ti, Hf, Zr, Nb, Ta,Ce, Pr, Nd, Gd, Dy, Yb, and Lu, in the additional oxide film 200 a, maybe diffused into the undoped Al₂O₃ film 302. The heat treatment processH allows the undoped Al₂O₃ film 302 to be doped with the diffused metalelements, thereby forming the doped Al₂O₃ film 300 described withreference to FIG. 1 . However, the process of forming the doped Al₂O₃film 300 is not limited to the example set forth above. In anotherexample, elements (aluminum (Al) and oxygen (O)) constituting an Al₂O₃film and an element (for example, hafnium (Hf) and/or zirconium (Zr))required to be doped into the Al₂O₃ film may be deposited in situ by anALD process, thereby forming the doped Al₂O₃ film 300. The doped Al₂O₃film 300 of the present disclosure may include two types of dopants (forexample, the first dopant and the second dopant, both described withreference to FIG. 1 ). However, the doped Al₂O₃ film 300 is not limitedto including two types of dopants. In another example, the doped Al₂O₃film 300 may include three or more types of dopants.

Referring again to FIG. 1 , the top electrode 400 may be formed on thedoped Al₂O₃ film 300. The top electrode 400 may be formed by adeposition process. For example, the top electrode 400 may be formed bya CVD process, a PVD process, or an ALD process. The top electrode 400may include a metal, a metal nitride, a metal oxide, or a combinationthereof. For example, the top electrode 400 may include TiN, MoN, CoN,TaN, W, Ru, RuO₂, SrRuO₃, Ir, lrO₂, Pt, PtO, (Ba,Sr)RuO₃ (BSRO), CaRuO₃(CRO), (La,Sr)CoO₃ (LSCO), or a combination thereof.

The present disclosure may provide a method of fabricating the capacitor1 that includes the doped Al₂O₃ film 300 including two types of dopants.

FIG. 10 is a flowchart illustrating a method of manufacturing a bottomelectrode that includes a metal nitride represented by MM′N. FIG. 11A isa conceptual diagram illustrating the method of manufacturing a bottomelectrode according to FIG. 10 . FIG. 11B is a conceptual diagramillustrating the method of manufacturing a bottom electrode according toFIG. 10 . FIG. 11C is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 . FIG. 11D is aconceptual diagram illustrating the method of manufacturing a bottomelectrode according to FIG. 10 . FIG. 11E is a conceptual diagramillustrating the method of manufacturing a bottom electrode according toFIG. 10 . FIG. 11F is a conceptual diagram illustrating the method ofmanufacturing a bottom electrode according to FIG. 10 . FIG. 11G is aconceptual diagram illustrating the method of manufacturing a bottomelectrode according to FIG. 10 . FIG. 11H is a conceptual diagramillustrating the method of manufacturing a bottom electrode according toFIG. 10 .

Referring to FIGS. 10, 11A, and 11B, the substrate SU may be prepared(S100).The substrate SU may have a target surface on which a bottomelectrode is to be formed. The substrate SU may include a semiconductormaterial pattern, an insulating material pattern, and a conductivematerial pattern. For example, the substrate SU may include thesubstrate 1100, the gate structure 1300, the interlayer dielectric 1400,and the contact 1500 of FIGS. 5 and 6 .

The substrate SU may be arranged in a reaction chamber, and then, afirst source including a metal organic ligand may be supplied into thereaction chamber (S110).The metal organic ligand may be represented byMRx including a metal element, M, and an organic ligand, R. Here, x maybe in a range of 0<×≤6. M may be one of Be, B, Na, Mg, Al, Si, K, Ca,Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo,Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg,Tl, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, and U. R may include at least one ofa C1-C1 0 alkyl group, a C2-C10 alkenyl group, a carbonyl group (C═O), ahalide, a C6-C10 aryl group, a C6-C10 cycloalkyl group, a C6-C10cycloalkenyl group, (C═O)R (where R is hydrogen or a C1-C10 alkylgroup), a C1-C10 alkoxy group, a C1-C10 amidinate, a C1-C10 alkylamide,a C1-C10 alkylimide, —N(Q)(Q′) (where Q and Q′ are each independently aC1-C10 alkyl group or hydrogen), Q(C═O)CN (where Q is hydrogen or aC1-C10 alkyl group), and a C1-C10 β-diketonate.

As a process of supplying the first source, an ALD process may be used.The ALD process may be performed at a temperature of about 100° C. toabout 500° C. The process temperature may be set according to thethermal stability of the metal organic ligand. Because a metal organicligand having low thermal stability may be decomposed at hightemperatures, an ALD process for the metal organic ligand having lowthermal stability may be performed at a temperature of about 400° C. orless.

The organic ligand, which is not adsorbed onto the substrate SU, in themetal organic ligand supplied into the reaction chamber may be removedby purging (S120).The purging is a process of discharging, out of thereaction chamber, the organic ligand not involved in a reaction, or theorganic ligand that is a by-product after involved in the reaction. Aninert gas such as Ar, He, Ne, or the like, or N₂ gas may be used for thepurging.

As shown in FIG. 11B, the metal organic ligand is adsorbed onto thesubstrate SU.

The processes of FIGS. 11A and 11B may be represented by the followingChemical Equations (1) and (2).

xMR₄ → xMR_(4-a) + x * aR

xMR_(4-a) + x * aR → xMR_(4-a)

Chemical Equation (2) indicates that the residual ligand component isremoved by the purging.

Next, it may be determined by a control device (not shown) whetheradditional supply of the source for MR_(x) is required (S130), andoperations S110 and S120 may be repeated as needed.

Referring to FIGS. 10, 11C, 11D, and 11E, a second source including ahalogen compound may be supplied into the reaction chamber (S140).As aprocess of supplying the second source, an ALD process may be used. TheALD process may be performed at a temperature of about 100° C. to about500° C. The process temperature may be set by taking into account thethermal stability of the metal organic ligand adsorbed onto thesubstrate SU. Because a metal organic ligand having low thermalstability may be decomposed at high temperatures, an ALD process for thehalogen compound may be performed at a temperature of about 400° C. orless.

The halogen compound may be represented by M′Ay (where y is a realnumber greater than 0) including a halogen element, A. A may include atleast one of F, Cl, Br, and l. y may be in a range of 0<y≤6. M′ may beone of H, Li, Be, B, N, O, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr,Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru,Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd,Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, lr, Pt, Au, Hg, Tl, Pb,Bi, Po, Fr, Ra, Ac, Th, Pa, and U.

Next, the organic ligand not reacting with the halogen compound may beremoved by purging (S150). An inert gas such as Ar, He, Ne, or the like,or N₂ gas may be used for the purging. In this operation, both thehalogen compound not involved in a reaction and a reaction by-productmay be removed.

Operation S140 of supplying the second source including the halogencompound and operation S150 of performing the purging are illustrated inFIGS. 11C to 11E and may be represented by the following ChemicalEquations (3) to (5).

yM’Cl₄ → yM’Cl_(4-b) + y*bCl

xMR_(4-a) + yM’Cl_(4-b) + y*bCl

 → xMCl_(4-a) + y M’Cl_(4-b) + x*(4-a)R +((y*b-x*(4-a))/2)Cl₂

xMCl_(4 − a) + y M’Cl_(4-b) + x*(4-a)R +((y*b-x*(4-a))/2)Cl₂

 → xMCl_(4-a) + y M’Cl_(4-b)

In the above Chemical Equations (3) to (5), Cl is given as an example ofthe halogen element, A, and Chemical Equation (5) indicates that theresidual ligand component and the reaction by-product are removed by thepurging.

As shown in FIG. 11E, M supplied from the first source and M′ suppliedfrom the second source are adsorbed onto the substrate SU while bondedto the halogen element, A.

Next, it may be determined whether additional supply of the source forM′Ay is required (S160), and operations S140 and S150 may be repeated asneeded.

Referring to FIGS. 10, 11F, 11G, and 11H, a nitridant may be suppliedinto the reaction chamber (S170). An ALD process may be used as aprocess of supplying the nitridant and may be performed at a temperatureof about 100° C. to about 500° C. The nitridant, which is a reaction gasincluding nitrogen, may include at least one of NH₃, N₂H₂, N₃H, andN₂H₄. The nitridant reacts with M bonded to the halogen element, A, andreacts with M′ bonded to the halogen element, A, and a metal nitridefilm, that is, MM′N, is formed on the substrate SU. Most of a reactionby-product including the halogen element is vaporized due to the processtemperature.

The supply of the nitridant and the reaction due to the nitridant areillustrated in FIGS. 11F to 11H and may be represented by the followingChemical Equation (6).

xMCl 4 -a + y M ′ Cl 4 -b + zNH c → M x M ′ y Z z + z*c HCl + x* 4 -a +y* 4 -b -z*c / 2 Cl 2

It may be checked whether a metal nitride film 101 is formed to adesired thickness, and operations S110 to S170 may be repeated as needed(S180).The metal nitride film 101 may be the bottom electrode 100described above.

In an example, after operation S170 of supplying the nitridant into thereaction chamber, a heat treatment may be additionally performed toremove the halogen element of the halogen compound, the halogen elementremaining as a reaction by-product. A temperature of the heat treatmentmay range from about 200° C. to about 1000° C.

In the metal nitride film 101 formed according to the above-describedoperations, the amount of impurities except for MM′N is extremely low.Because almost all of the organic ligands included in the source usedfor the formation of MM′N are removed, there are almost no carbonimpurities in the metal nitride film 101. This is as shown in theprocesses according to Chemical Equations (1) to (6). The carbonimpurities may be present in an amount of about 1% or less in the metalnitride film 101 formed according to those processes. On the other hand,according to existing methods, ligands or reaction by-products have nochoice but to remain. A metal nitride film has higher resistivity withan increasing amount of impurities and thus is not suitable to functionas an electrode. The value of resistivity of the metal nitride film mayvary by up to a factor of several hundreds depending upon the amount ofimpurities. The metal nitride film, MM′N, which is manufactured by themethod according to an embodiment and thus includes almost noimpurities, may have a low value of resistivity and may be used as anexcellent electrode material. In an example, the metal nitride film 101may be the bottom electrode 100 shown in FIGS. 1, 4, 5, 6, 7, 8, and 9 .

The method of manufacturing a bottom electrode including a metalnitride, according to the present disclosure, does not include directlyreacting a metal organic ligand with a nitridant, and thus, the bottomelectrode including the metal nitride having better quality may beformed.

FIG. 12 is a schematic diagram for an electronic device including acapacitor according to some embodiments.

Referring to FIG. 12 , an electronic device 900 according to exampleembodiments of inventive concepts may be a personal digital assistant(PDA), a laptop computer, a portable computer, a web tablet, a wirelessphone, a mobile phone, a digital music player, a cable/wirelesselectronic device, etc., but is not limited thereto. The electronicdevice 900 may include a controller 910, an input/output (l/O) device920 (e.g., a keypad, a keyboard and/or a display), a memory device 930,and a wireless interface unit 940 which are combined with each otherthrough a data bus 950. The controller 910 may be implemented withprocessing circuitry processing circuitry such as hardware includinglogic circuits; a hardware/software combination such as a processorexecuting software; or a combination thereof. For example, theprocessing circuitry more specifically may include, but is not limitedto, a central processing unit (CPU), a microprocessor, a digital signalprocessor, a microcontroller or other logic devices. The other logicdevices may have a similar function to any one of the microprocessor,the digital signal processor and the microcontroller. The memory device930 may store, for example, commands performed by the controller 910.Additionally, the memory device 930 may also be used for storing a userdata.

The memory device 930 includes a plurality of memory cells MC. Each ofthe memory cells MC may include a capacitor C connected to a transistorTR. A word line WL may be connected to a gate of the transistor TR. Abit line BL may be connected one source/drain region of the transistorTR and the capacitor C may be connected to the other source/drain regionof the transistor TR. The other end of the capacitor C may be connectedto a power supply voltage Vdd. The capacitor C may include thecapacitors 1 and/or 2 described in FIGS. 1, 4, 5, and 6 of the presentapplication.

The electronic device 900 may use the wireless interface unit 940 inorder to transmit data to a wireless communication network communicatingwith a radio frequency (RF) signal or in order to receive data from thenetwork. For example, the wireless interface unit 940 may include anantenna or a wireless transceiver. The electronic device 900 may be usedin a communication interface protocol such as a third generationcommunication system (e.g., CDMA, GSM, NADC, E-TDMA, WCDAM, and/orCDMA2000).

FIG. 13 is a schematic diagram of a memory system including a capacitoraccording to some embodiments.

FIG. 13 is a schematic block diagram illustrating a memory system.Referring to FIG. 13 , a memory system 1000 may include a memory device1010 for storing data and a memory controller 1020. The memorycontroller 1020 may read or write data from/into the memory device 1010in response to read/write request of a host 1030. The memory controller1020 may make an address mapping table for mapping an address providedfrom the host 1030 (e.g., a mobile device or a computer system) into aphysical address of the memory device 1010. The memory controller 1020may be implemented with processing circuitry processing circuitry suchas hardware including logic circuits; a hardware/software combinationsuch as a processor executing software; or a combination thereof. Forexample, the processing circuitry more specifically may include, but isnot limited to, a central processing unit (CPU) , an arithmetic logicunit (ALU), a digital signal processor, a microcomputer, a fieldprogrammable gate array (FPGA), a System-on-Chip (SoC), a programmablelogic unit, a microprocessor, application-specific integrated circuit(ASIC), etc. The memory device 1010 may include a plurality of memorycells MC. Each of the memory cells MC may include a capacitor Cconnected to a transistor TR, and may have structure that is the same asthe memory cell MC described in FIG. 10 . The capacitor C may includethe capacitors 1 and/or 2 described in FIGS. 1, 4, 5, and 6 of thepresent application.

The present disclosure may provide a capacitor having improvedproperties of leakage current and capacitance.

The present disclosure may provide a method of fabricating a capacitorhaving improved properties of leakage current and capacitance.

The present disclosure may provide a semiconductor device including acapacitor having improved properties of leakage current and capacitance.

However, the present disclosure is not limited to the above-describedaspects.

It should be understood that embodiments described herein should beconsidered in a descriptive sense only and not for purposes oflimitation. Descriptions of features or aspects within each embodimentshould typically be considered as available for other similar featuresor aspects in other embodiments. While one or more embodiments have beendescribed with reference to the figures, it will be understood by thoseof ordinary skill in the art that various changes in form and detailsmay be made therein without departing from the spirit and scope asdefined by the following claims.

What is claimed is:
 1. A capacitor, comprising: a bottom electrode; atop electrode over the bottom electrode; a dielectric film between thebottom electrode and the top electrode; and a doped Al₂O₃ film betweenthe top electrode and the dielectric film, the doped Al₂O₃ filmincluding a first dopant, an oxide including a same element as the firstdopant having a higher dielectric constant than a dielectric constant ofAl₂O₃; and an interfacial film between the bottom electrode and thedielectric film, wherein the interfacial film comprises an oxidecomprising a metal element that is included in the bottom electrode. 2.The capacitor of claim 1, wherein the bottom electrode comprises a metalnitride represented by MM′N, the interfacial film comprises a metaloxynitride represented by MM′ON, M is a metal element, M′ is an elementthat is different from M, N is nitrogen, and O is oxygen.
 3. Thecapacitor of claim 2, wherein the bottom electrode comprises carbonimpurities in an amount of greater than 0 % and less than or equal to 1%.
 4. The capacitor of claim 2, wherein M is Be, B, Na, Mg, Al, Si, K,Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb,Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au,Hg, TI, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, or U.
 5. The capacitor of claim2, wherein M′ is H, Li, Be, B, N, O, Na, Mg, Al, Si, P, S, K, Ca, Sc,Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb,Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au,Hg, Tl, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, or U.
 6. The capacitor of claim2, wherein the metal nitride is represented by M_(x)M′_(y)N_(z),0 < x ≤ 2, 0 < y ≤ 2, and 0 < z ≤
 4. .